Preparation of metal petroleum sulfonates



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United States Patent @fiice 2,947,694 Patented Aug. 2, 1960 PREPARATION OF METAL PETRGLEUM SULFGNATES James T. Gragson, Bartlesviile, Okla, assignor to Phillips Petroleum Company, a corporation of Delaware No Drawing. Filed Oct. 6, 1955, Set. N 539,023

9 Claims. (Cl. 2523'3) This invention relates to metal organic sulfonates. In one aspect, it relates to an improved method for preparing organic sulfonic acid derivatives from petroleum. In another aspect it relates to a method for the concentration and improvement of an oil solution of a metal petroleum sulfonate whereby a highly active detergent is produced having particular applicability as additive rnaterial in lubricating oils. In a further aspect it relates to improved lubricating oils containing novel detergent additives.

At the present time it is common practice to enhance or modify certain of the properties of lubricating oils through the use of various additives or improvement agents. The lubricating oils employed in internal combustion engines, such as automotive, light aircraft, and diesel engines in particular, require the use of additive agents to render them serviceable under the adverse environmental conditions encountered in these engines. Among the various additives employed in modern engine oils, one of the most important is the type Which acts to prevent accumulation of sludge in the crankcase and on the cylinder Walls, thereby preventing sticking of the piston rings, and the formation of varnish-like coating on the pistons and cylinder walls. Because of their general function of maintaining a clean engine, additives of this nature are termed detergents, although it is now understood that they have little utility in cleaning a dirty engine but by virtue of dispersant activity prevent or greatly retard engine fouling.

Many petroleum sulfonic acid derivatives have been employed in the past as detergent additives for lubricating oils. Because of the complexity of petroleum, the exact chemical nature of its sulfonic acid derivative is very difficult to ascertain accurately. The source of the crude petroleum used in the production of sulfonic acids and their derivatives is one of the several variables which determine the predominant organic nature of the latter, i.e., parafiinic, naphthenic, or aromatic. In the absence of chemical analysis, the sulfonates are usually classified according to their relative solubility in oil and the particular stock material from which they are made.

Specific alkaline earth metal-containing detergents such as barium or calcium sulfonates or phenates have been Widely used in the past and these have served satisfactorily in many cases for imparting detergent properties to mineral oils. The petroleum fractions used in preparing these prior art sulfonates and phenates are mostly unrefined or semi-refined base oil stocks of relatively low viscosity and relatively low molecular weight. The base oil used in the preparation of such sulfonates is often a naphthenic oil of SAE 10W or 20 viscosity grade having molecular weights in the order of 300 to 500. Conventional methods for preparing petroleum sulfonates from these unrefined, low molecular weight base oils remove an acid sludge from the sulfonation mixture. When high molecular weight, highly refined Oils are employed in the preparation of petroleum sulfonates, an acid sludge usually does not separate from the reaction mixture.

Improved metal petroleum sulfonates have recently been derived from high molecular weight hydrocarbons by a method such as disclosed and claimed in the US. application Serial No. 478,839, filed December 30, 1954, and now abandoned by William B. Whitney. In the process set forth therein, highly refined, solvent extracted, high molecular weight petroleum stocks are treated with a sulfonating agent, the reaction product is neutralized with anhydrous ammonia, the resulting ammonium petroleum sulfonate is extracted with an organic solvent, such as alcohol, and is converted to the metal petroleum sulfonate by reaction with an excess of :a metal salt or hydroxide. While the metal petroleum sulf'onates obtained by the practice of the invention set forth in the aforementioned application by Whitney may be advantageously employed as detergents in lubricating oils, the oil-dispersed active component obtained, i.e., the metal petroleum sulfonate, is not as concentrated in the oil phase as may be desired in some applications. When an attempt is made to concentrate these metal petroleum sulfonates by solvent extraction, for example, with methyl isobutyl ketone, a low molecular weight fraction difficultly soluble in oil settles out and this fraction is virtually impossible to get back into solution or blend into a lubricating oil.

Accordingly, I have found that concentrated metal petroleum sulfonates may be produced from the metal petroleum sulfonate-oil solution of aforementioned Whitney application by solvent separating the same with an organic solvent, such as methyl isobutyl ketone (hereinafter abbreviated MIBK), cooling the resultant mixture and stratifying the resultant immiscible phases, Withdrawing the MIBK oil-insoluble metal petroleum sulfonate phase therefrom, and treating the latter with a small amount of an acid having an ionization constant greater than l Illsuch as hydrochloric acid, sulfuric acid, acetic acid and the like, rendering the metal petroleum sulfonate oil-soluble and thus increasing the yield of usable additive. The well known and extensive utility of refined petroleum sulfonates makes it commercially important that the sulfonates obtained be in a concentrated form, particularly when the "factors of transportation and storage are considered. The oil solution of my invention containing the concentrated oil-soluble metal petroleum sulfonate can be conveniently-stored and transported and later can be readily mixed or blended with any lube oil stock, such as SAE-lOW, 20 or 30, and the mixtureor blend employed as a lubricating oil having very desirable lubricating properties.

An object of this invention is to provide concentrated oil solutions of oil-soluble metal petroleum sulfonates.

Another object is to provide concentrated additive agents for imparting improved lubricating properties to lubricating oils.

A further object is to providea method for preparing an improved lubricating .oil having desirable detergent and dispersant properties and a high ash content.

. A still further object is to prevent the accumulation of oil degradation products on oil lubricated engine parts, such as pistons and cylinderwalls, and to prevent accumulation of crankcase sludge, especially undercold engine, stop and go conditions.

Other objects, advantages and features of this invention will become apparent to those skilled in the art I prefer to employ deasphalted and solvent-refined petroleum fractions having a viscosity between about 120 and 700 SUS at 210 F. and an average molecular weight of about 640 to 1,300, and more preferably petroleum fractions having a viscosity between about 150 and-600 SUS at 210 F. and an average molecular weight of about '675 to 900. A-specifically preferred sulfonation stock is a propane-fractionated, solvent-extracted and de-waxed Mid-Continent oil of about 200 to 230 SUS at 210 F. having a viscosity index of about 85 to 95 or even higher.

'Sulfonating agents which are known to the art can be utilized in the sulfonation step of my novel process including fuming sulfuric acid, chlorosulfonic acid and sulfur trioxide. Fuming sulfuric acid is the preferred sulfonating agent and is particularly adapted to this novel process for producing oil-soluble metal petroleum sulfonates of high molecular weight. The fuming sulfuric acid can vary from 10 weight percent excess S to 40 weight percent S0 however, I prefer to use commercial fuming sulfuric acid, (which has about 20 weight percent excess S0 All metals are suitable for preparing these metal petroleum sulfonates. Metals which are particularly suitable for preparing the metal petroleum sulfonates of this invention include barium, calcium, lithium, potassium, nickeLcobalt, cadmium, silver, iron, aluminum, copper, magnesium, lead, beryllium, mercury, sodium, tin, and zinc. The alkaline earth metals are preferred and barium and, more especially, calcium are specifically preferred in the practice of this invention.

Sulfo-nation temperatures are usually controlled within the range of about 50 to 200 F. with the preferred operating range being between 80 and 150 F. Somewhat lower temperatures can be employed without seriously slowing the reaction rates, but no particular advantage results from operating in this manner and it is advantageous to sulfonate at the elevated temperatures, i.e., 50 to 200 F., in order to reduce the time required for the sulfonation step. At temperatures above about 200 F., excessive oxidation with liberation of sulfur dioxide takes place. The oil-acid ratio varies with the sulfonation temperature but generally can be in the range of from 1 to 0.175 and 1 to 0.7. The sulfonation reaction is usually carried out at atmospheric pressure although pressures greater or less than atmospheric can be employed if desired. a

The neutralization step is usually accomplished by countercurrent contact of the oil mixture resulting from the sulfonation step with anhydrous ammonia and the contacting step is conveniently accomplished by bubbling the ammonia through the oil mixture. The neutralization step can also be accomplished in pressure equipment with liquidammonia in which case the oil and the ammonia are contacted by countercurrent flow, for example, through a bubble plate column.

The ammonium petroleum sulfonates are then extracted from the oil with a polar solvent such as isopropyl alcohol, ethyl acetate, butyl alcohol, n-propyl alcohol, and the like, by conventional liquid-liquid solvent extraction methods. The extract is then contacted with an aqueous solution or slurry of the salt, hydroxide oroxide of the metal at a temperature of 200 to 400 F; and at a pressure suflicient to prevent evaporation of the volatile materials present. The extract is thus con tacted for a period of time generally in the range of 30 minutes to 5 hours. If the salt solutionis used, it is preferred to make a final contacting with the hydroxide until a sample of the product upon heating to 500 F. evolves vapors which are not acidic as determined by a test with moist litmus paper.-

Although the foregoing is the preferred procedure to be followed for preparing the unconcentrated metal petroleum sulfonates difficultly soluble in oil, it is merely illustrative and any procedure which results in such a 4 product can be advantageously subsequently treated according to my invention.

To the stabilized product prepared by the above procedure, which contains a fraction difiicultly soluble in such hydrocarbon solvents such as pentane, I propose by the practice of my invention to add an organic solvent, such as methyl isobutyl ketone, in about a 10.5 :1 solvent-to-oil ratio, heat the resultant solution to 210 F. and stir until the sulfonate dissolves. The solvent-oil ratio will depend somewhat on the particular lubricating oil stock and is such that both the oil and the petroleum sulfonates are dissolved at elevated temperature. Generally the solvent-oil ratio will be in the range between 2:1 and 20:1. Other solvents which can be employed in place of MIBK as the selective solvent are, for example, methyl isopropyl ketone, methyl ethyl ketone, and like ketones having at least 4 carbon atoms and preferably 4 to 8 carbon atoms per molecule. After solution is complete, the solution is cooled and the resulting two immiscible layers are separated. Amultistep cooling procedure is the preferred separation method and this can be done in steps such as cooling first to about 60 F. and separating the resulting immiscible phases, and subsequently cooling the top phase to 20 F. and making further separation of the resulting immiscible phases. If a stepwise cooling is effected and the solution cooled to about 60 F., the initial bottom phase will contain the normallysolid heavy oil-soluble petroleum sulfonates in a concentrated state. The initial top phase will contain oil-insoluble petroleum sulfonates in MIBK and oil. This initial top phase is subsequently cooled to a lower temperature, for example 20 F., and the resulting immiscible layers again separated. The resulting second top phase will comprise mainly a solution of MIBK in oil and will contain a small amount of oil-insoluble petroleum sulfonate therein. The resulting second bottom phase will comprise oil-insoluble petroleum sulfonates in MIBK. While it is preferred to cause the stratification of the immiscible liquid phases by cooling, it is obvious that other means for causing stratification can be applied, for example, using anti-solvents. When cooling is employed, the separation of the oil-insoluble metal petroleum sulfonates can be accomplished by a one step cooling procedure by cooling, for example to 20 F. However, it is preferred to employ a multi-step cooling procedurein order to obtain a better separation into oilsoluble and oil-insoluble fractions; a first cooling step generally employed can be carried out to about 50-70? 'F. and the second cooling step to. about l030 F., for

example.

It is to be understood that by the term oil-insoluble? as used in the discussion, example and appended claims, I intend to describe those solutions which are difficultly soluble in oil, since no quantitative measurements of solubility were performed.

Regardless of the method used to remove the oil from the oil-sulfonatemixture (in order to concentratethe sulfonate), the concentrated sulfonate cannot bereadily redissolved completely in oil. For example, when the multi-step cooling procedure outlined above is employed, the second bottom phase is difficultly soluble in oil., This difiicultly soluble material, whether separated from the oil-soluble fraction or not, is rendered readily soluble in oil by the practice of my invention.

When the multi-step cooling procedure is employed, the second bottom phase containing oil-insoluble metal petroleum sulfonate is subsequently treated with an acid, rendering the sulfonates oil-soluble. The resultant oil solution of metal petroleum sulfonate in concentrated form can be combined and mixed with the heavy'oil-' solublepetroleum sulfonates from the first separation (i.e., in the initial bottom phase) and the whole added to a mineral or lubricating oil, or these concentrated sul-.

mineral or lubricating oil. Generally, the finished lubricating oils provided by this invention comprise from about 0.1 .to weight percent of concentrated oil-solublemetal petroleum sulfonate and preferably 1 to 12 weight percent.

The quantity of acid I propose to treat the oil-insoluble petroleum .sulfonate with is very small and much less than an equivalent amount. Generally this quantity will be about one gram of acid for every 100-1000 grams, preferably for every 200-800 grams, of oil-insoluble petroleum sulfonate (i.e., the fraction which is soluble in MIBK at 60 F. and insoluble at F.). Since the amount of acid employed will vary with the particular hydrocarbon fraction sulfonated, etc., it is preferred to give the real limits of a small but effective amount necessary to solubilize the oil-inso1ub1e metal petroleum sulfonate. In treating the oil-insoluble petroleum sulfonate with acid, care must be taken to prevent the acid from deleteriously affecting the desired detergent properties of the additive. For example, because of the well known oxidizing properties of concentrated nitric acid, it will be apparent to those skilled in the art upon practicing my invention that this acid must not be used at elevated temperatures. The acid I prefer to employ is dry hydrogen chloride gas, though other acids such as hydrogen bromide, sulfuric acid, acetic acid and like .acids having an ionization constant greater than 1 10- can be employed.

The advantages of this invention are illustrated in the following example. The reactants and their proportions and their specific ingredients are presented as being typical and should not be construed to unduly limit the invention.

EXAMPLE A reaction vessel equipped with a stirrer and a circulationpump was charged with 180.7 pounds of a solvent refined, deasphalted and de-waxed lubricating oil stock derived from Mid-Continent crude petroleum and having the following properties: a viscosity of 4278 SUS at 100 F., a viscosity of 203 SUS at 210 F., and a viscosity index of 93. To this was added with stirring 36 pounds of 20 weight percent fuming sulfuric acid. During the period of acid addition, the temperature rose from 73 to 97 F. The mixture was stirred for an hour after the acid addition, diluted with 5 gallons of pentane, and 11.5 pounds of anhydrous ammonia was then bubbled through the mixture, which resulted in complete neutralization of the acid present. After neutralization the neutralized mixture was heated to 134 F. so asto remove the major portion of pentane and 23.2 gallons of isopropyl alcohol was added to the mixture, amounting to 29.8 gallons, and stirred while the mixture was warmed to 154 F. After settling overnight the alcohol phase, amounting to 17.3 gallons, was withdrawn, and 16.6 gallons of isopropyl alcohol was added to the residue with agitation while the mixture was warmed. to 165 F. The alcohol phase, 23.3 gallons, Was withdrawn at 160 F. after settling had occurred and 19.3 gallons of fresh alcohol was added to the residue with stirring and the solution was again warmed to 165 F. and allowed to settle. After settling the alcohol phase, amounting to 26.8 gallons, was removed from the residue at 165 F. The fourth extraction was inade with 14.6 gallons of isopropyl alcohol at 170 F. and 16 gallons of alcohol phase was recovered. The total alcohol extracts were combined and partially stripped of alcohol so that the final mixture contained 54.5 weight percent ammonium sulfonate and oil and 45.5 weight percent alcohol. This alcohol-extracted ammonium petroleum sulfonate oil solution was a dark brown, viscous mixture. A solvent-free sample of the sulfonate oil solution analyzed 1.07 percent nitrogen.

About pounds of the ammonium petroleum sulinnate oil solution prepared above were dissolved in 15 pounds of isopropyl alcohol and 10 gallons of pentane and to this mixture was added a solution of 6 pounds of barium chloride and 16 pounds of water. The mixture was agitated for several hours after which the water layer was drawn off and the oil layer was again agitated for several minutes with 15 pounds of fresh water and allowed to settle. The water layer was then removed and the oil layer was contacted for 30 minutes with 2.1 pounds of barium chloride in 31 pounds of water. After standing overnight, the water layer was withdrawn and the emulsion, which had formed, was broken by addition of 18.5 pounds of pentane and 7 pounds of isopropyl alcohol. The oil layer was removed, filtered and stripped of solvent leaving 25 pounds of barium petroleum sulfonate in oil. The barium sulfonate additive evolved acidic vapors when subjected to the previously mentioned acid vapor test and was stabilized by the addition of dry barium hydroxide and then by heating to 200 F. for several minutes followed by filtering to remove excess barium hydroxide and inorganic products. The stabilized product did not evolve acidic vapors when heated to 500 F. This stabilized product was a viscous fluid and had an ash content of 10.8 weight percent.

The stabilized product was mixed with MIBK in a 10.5:1 solvent-to-oil ratio, heated to 210 F. and stirred un-tii the sulfonate and oil dissolved. The solution was allowed to stand until it cooled to 59 F,. and the resinous bottom phase was then withdrawn. This bottom phase amounted to 31 weight percent of the charge on a solvent-free basis and contained concentrated, oilsoluble, MIBK insoluble (at 59 F.) barium petroleum sulfonate in oil. The oily, viscous fluid top phase contained oil-insoluble barium petroleum sulfonate in MIBK and oil. The top phase was cooled to 20 F. (during 48 hours) and a second bottom phase which separated was withdrawn from a second resulting top phase which contained oil and a small amount of insoluble sulfona-te. Eighty grams of the second bottom phase which comprised a barium petroleum sulfonate fraction insoluble in MIBK at 20 1 was freed of excess MIBK by washing with acetone, the solvent was removed, and the dry sulfonate was dispersed in pentane. The material was insoluble and became jelly-like. A small amount, less than 1 gram per 400 grams of material, of dry hydrogen chloride was passed through the pentane until the sulfonate had completely dissolved. The pentane solution was diluted with grams of a 10 stock lubricating oil (with viscosity of about 40 SUS at 210 F.) and natural gas passed through to remove excess hydrogen chloride. The pentane was evaporated off.

The oil solution of metal petroleum sulfonatc obtained by the hydrogen chloride treatment of the MIBK insol-' uble sulfonate was evaluated as a lubricating oil additive in a simulated L-l Lauson engine test such as described in Motor Oils and Engine Lubrication by Carl W. Georgi, beginning at page 83. The operation conditions which were utilized in this test have been modified and are as follows: The engine Was operated under a 1.2 horsepower load at 1600::20 r.p.n1., maintaining a cooling jacket temperature of 300 R, an oil temperature of 225 R, an air-to-fuel ratio of 13.521, carburetor air at room temperature, spark advance of 25 BTDC, and crankcase vacuum of 1.0 inch of mercury. At the end of 60 hours engine operation under these conditions the engine was stopped, disassembled, and the piston and bearings were examined.

The lubricating oil employed as a base oil in this test was a solvent-refined Mid-Continent oil having a viscosity of about 40 SUS at 210 F. The additive material, 3.12 weight percent of active metal petroleum sulfonate, was dissolved in the base oil and no corrosion inhibitor was added. As a standard for further evaluation of the blend of lubricating oil and the oil-soluble Table I Piston Bearing Percent Concentration of Sulfona-te Varnish Corrosion,

None (Base Oil) 6.0 182 3.12 8.3 59.2

These data show that the oil-solubilized metal petroleum sulfonates of the instant invention can be advantageously employed as detergents in lubricating oils. The barium petroleum sulfonate additive, as illustrated in the above table, not only increased the piston cleanliness from 6.0 to 8.3 but at the same time reduced the bearing corrosion from 182 mg. to 59.2 mg. This is particularly advantageous since commercial corrosion inhibitors decrease the piston varnish rating. Moreover, the reduction in bearing corrosion indicates that the hydrogen chloride does not remain in the treated oil-insoluble petroleum sulfonate and corrode the bearmgs.

In reiteration, advantages of my invention are the manufacture of a detergent which has particular application as a good additive for lubricating oils; the production of a detergent which reduces piston varnish; the produc tion of a detergent which reduces bearing corrosion; the production of a detergent having a high ash content; the production of an oil solution of a concentrated metal petroleum sulfonate; and the production of a detergent which is chemically compatible with lubricating oil. The additive product prepared according to my invention contains an extremely high concentration of the metal petroleum sulfonate thereby permitting the employment of a smaller amount of material for a given application.

Variations and modification of my invention will become apparent to those skilled in the art without departing from the scope or spirit of my invention, the essence of which is the discovery of a method for producing a concentrated metal petroleum sulfonate oil solution by treating an oil-insoluble metal petroleum sulfonate with a small but effective amount of an acid, thereby rendering the sulfonate oil-soluble, which concentrates may be advantageously employed as detergent additives in lubricating oils although the utility of my novel detergents is not limited hereto.

I claim:

1. In a method for producing a material having detergent and dispersant properties which comprises sulfonating a hydrocarbon fraction having a viscosity between about 120 and 700 SUS at 210 F., neutralizing the resulting sulfonic acids with ammonia, extracting the resultant neutralized sulfonation mixture with a liquid organic solvent, and converting the resultant ammonium petroleum sulfonates to metal petroleum sulfonates, theimprovement comprising adding to said metal petroleum sulfonates a selective solvent to cause the formation of two immiscible layers including a bottom layer containing oil-insoluble metal petroleum sulfonates, said selective 700'SUS at 210 F., neutralizing the resulting sulfonic acids with ammonia, extracting the resulting ammonium petroleum'sulfonates with a liquid organic solvent, and converting said ammonium petroleum sulfonates to metal petroleum sulfonates, the improvement comprising adding a selective solvent to said metal petroleum'sulfonates and cooling the resultant mixture to cause the formation of two immiscible layers including a bottom layer containing preferentially oil-insoluble metal petroleum sulfonates, said selective solvent consisting of an aliphatic liquid ketone having at least four carbon atoms per molecule, isolating said bottom layer and treating the same with an acid having an ionization constant greater than 1X10- in anamount sufficient to render oil-soluble said oilinsoluble metal petroleum sulfonates, and recovering the resultant oil-soluble metal petroleum sulfonates as a product of the process. 7

3. The method according to claim 2 wherein said ammonium petroleum sulfonates are converted to said metal petroleum sulfonates by reaction with a metal compound selected from the group consisting of the salts, oxides, and hydroxides of alkali metals and alkaline earth metals.

'4. The method according to claim 2 wherein said acid is dry hydrogen chloride gas, one gram of which is employed per -1000 grams of said oil-insoluble metal petroleum sulfonate. 1

5. The method according to claim 2 wherein said organic solvent is isopropyl alcohol and said ketone is methyl isobutyl ketone.

6. The method according to claim 2 wherein said metal petroleum sulfonate is barium petroleum sulfonate.

7. A method according to claim 2 wherein said metal petroleum sulfonate is calcium petroleum sulfonate. 1

8. In a method for producing a material having detergent and dispersant properties which comprises sulfonating a deasphalted and solvent-refined petroleum bright stock having a viscosity between about and 700 SUS at 210 F., neutralizing the resulting sulfonic acids with ammonia, extracting the resulting ammonium petroleum sulfonates with isopropyl alcohol, and cons verting said ammonium petroleum sulfonates to alkaline earth metal petroleum sulfonates, the improvement comprising adding to said alkaline earth metal petroleum sulfonates a selective solvent consisting of methyl iso butyl ketone in about a ratio between 2: land 20: 1, cooling the resulting mixture to cause the formation of two immiscible layers including a bottom layer containing preferentially oil-insoluble alkaline earth metal petroleum sulfonates, isolating said bottom layer and treating the same with an acid having an ionization constant greater than 1 1O and in an amount sufficient to render oilsoluble said oil-insoluble alkaline earth metal petroleum sulfonates, and recovering the resulting oil-soluble alkaline earth metal petroleum sulfonates as the product of the process.

9, In a method for producing a material having de-. tergent and dispersant properties which comprises sul fonating a propane-fractionated, solvent-extracted and dewaxed Mid-Continent crude distillate having aviscosity in the range of 200-230 SUS at 210 F., neutralizing the resulting sulfonic acids with anhydrous ammonia, extracting the resulting ammonium petroleum sulfonates with isopropyl alcohol, and converting said ammonium petroleum sulfonates to alkaline earth metal petroleum sulfonates by reaction with a metal compound selected from the group consisting of the salts, oxides, and hydroxides of alkali metals and alkaline earth metals, the improvement comprising dissolving the resulting metal petroleum sulfonates in methyl isobutyl ketone, cooling the resulting admixture to a temperature in the range of 50-70' F. to cause the same to stratify into two immiscible layers including a top layer comprising preferentially oil-insoluble metal petroleum sulfonates, isolating said top layer and cooling the same to a temperature in the range 9 19-30 to cause the same to stratify to two im- References Cited in the file of this patent UNITED STATES PATENTS 2,514,733 Vold et a1. July 11, 1950 2,532,997 Cohen Dec. 5, 1950 2,535,101 Sproule et a1. Dec. 26, 1950 2,578,657 Anderson Dec. 18, 195 1 15 10 Axe et a1. Nov. 24, 1953 Lauer Ian. 18, 1955 Whitney June 7, 1955 Clarke et al July 12, 1955 Clarke July 12, 1955 Stewart et a1. Nov. 8, 1955 Asseff et a1. Nov. 8, 1955 Brown et a1 Dec. 20, 1955 Anderson et al Mar. 13, 1956 Roessler Mar. 27, 1956 Hutto et a1. lluly 31, 1956 Le Suer Aug. 28, 1956 Hutchings et a1. Dec. 3, 1957 Gragson Feb. 4, 1958 

1. IN A METHOD FOR PRODUCING A MATERIAL HAVING DETERGENT AND DISPERSANT PROPERTIES WHICH COMPROSES SULFONATING A HYDROCARBON FRACTION HAVING A VISCOSITY BETWEEN ABOUT 120 AN 700 SUS AT 210*F., NEUTRALIZING THE RESULTING SULFONIC ACID WITH AMMONIA, EXTRACTING THE RESULTANT NEUTRALIZED SULFONATION MIXTURE WITH A LIQUID ORGANIC SOLVENT, AND CONVERTING THE RESULTANT AMMONIUM PETROLEUM SULFONATES TO METAL PETROLEUM SULFONATES, THE IMPROVEMENT COMPRISING ADDING TO SAID METAL PETROLEUM SULFONATESA SELECTIVE SOLVENT TO CAUSE THE FORMATION OF TWO IMMISCIBLE LAYERS INCLUDING A BOTTOM LAYER CONTAINING OIL-INSOLUBLE METAL PETROLEUM SULFONATES, SAID SELECTIVE SOLVENT CONSISTING OF AN ALIPHATIC LIQUID KETONE HAVING AT LEAST FOUR CARBON ATOMS PER MOLECULE, ISOLATING SAID BOTTOM LAYER AND TREATING THE SAME WITH AN ACID HAVING AT IONIZATION CONSTANT GREATER THAN 1X10-5 IN AN AMOUNT SUFFICIENT TO RENDER OIL-SOLUBLE SAID OIL-INSOLBLE METAL PETROLEUM SULFONATE.
 9. IN A METHOD FOR PRODUCING A MATERIAL HAVING DETERGENT AND DISPERSANT PROPERTIWS WHICH COMPRISES SULFONATING A PROPANE-FRACTIONATED, SOLVENT-EXTRACTED AND DEWAXED MID-CONTINENT CRUDE DISTILLATE HAVING A VISCOSITY IN THE RANGE OF 200-230 SUS AT 210*F., NEUTRALIZING THE RESULTING SULFONIC ACIDS WITH ANHYDROUS AMMONIA, EXTRACTIN THE RESULTING AMMONIUM PETROLEUM SULFONATES WITH ISOPROPYL ALCOHOL, AND CONVERTING SAID AMMONIUM PETROLEUM SULFONATES TO ALKALINE EARTH METAL PETROLEUM SULFONATES BY REACTION WITH A METAL COMPOUND SELECTED FROM THE GROUP CONSISTING OF THE SALTS, OXIDES, AND HYDROXIDES OF ALKALI METALS AND ALKALINE EARTH METALS, THE IMPROVEMENT COMPRISING DISSOLVING THE RESULTING METAL PETROLEUM SULFONATES IN METHYL ISOBUTYL KETONE, COOLING THE RESULTING ADMIXTURE TO A TEMPERATURE IN THE RANGE OF 50-70*F. TO CAUSE THE SAME TO STRATIFY INTO TWO IMMISCIBLE LAYERS INCLUDING A TOP LAYER COMPRISING PREFERENTIALLY OIL-IM SOLUBLE METAL PETROLEUM SULFONATES, OSOLATING SAID TOP LAYER AND COOLING THE SAME TO A TEMPERATUE IN THE RANGE OF 10-30*F. TO CAUSE THE SAME TO STRATIFY TO TWO IMMISCIBLE LAYERS INCLUDING THE BOTTOM LAYER COMPRISING SAID PREFERENTIALLY OIL-INSOLUBLE METAL PETROLEUM SULFONATES, ISOLATING SAID BOTTOM LAYER AND TREATING THE SAMEWITH ONE GRAM OF DRY HYDROGEN CHLORIDE GAS PER 200-800 GRAMS OF SAID OIL-INSOLUBLE METAL PETROLEUM SULFONATES, AND RECOVERING THE RESULTING OIL SOLUBLE METAL PETROLEUM SULFONATES. 